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| United States Patent |
5,015,537
|
|
Uchiyama
, et al.
|
May 14, 1991
|
Ornamental member
Abstract
An improved ornamental member including at least two types of Cr or Ti hard
films of different color tones disposed by ion plating on a substrate is
prepared. The laminate includes a combination of Cr and Ti hard films
including a stainless steel colored Cr hard film layer containng Cr, N and
C as the main constituents, a gold colored Ti hard film having Ti and N as
the main constitutents, a dark grey Ti hard film having Ti, N and C as the
main constituents, a blue Ti hard film having Ti and O as the main
constituents and a brown Ti hard film having Ti, O and C as the main
constituents. The thickness of a single year of hard film is between about
0.2 and 1.5 .mu.m and the total film thickness at the laminated portion is
less than about 3 .mu.m. Preferably, each hard film layer is between about
0.2 and 0.8 .mu.m.
| Inventors:
|
Uchiyama; Akira (Suwa, JP);
Imai; Kiyohiro (Suwa, JP)
|
| Assignee:
|
Seiko Epson Corporation (Tokyo, JP)
|
| Appl. No.:
|
405243 |
| Filed:
|
September 11, 1989 |
Foreign Application Priority Data
| Sep 12, 1988[JP] | 63-227812 |
| Sep 13, 1988[JP] | 63-229612 |
| Jun 09, 1989[JP] | 1-147721 |
| Current U.S. Class: |
428/623; 428/336; 428/472; 428/627; 428/632; 428/698; 428/699 |
| Intern'l Class: |
B32B 015/04 |
| Field of Search: |
428/623,627,628,629,632,660,666,667,336,472,698,699
|
References Cited
U.S. Patent Documents
| Re32111 | Apr., 1986 | Lambert et al. | 428/699.
|
| 3964937 | Jun., 1976 | Post et al. | 428/699.
|
| 4101703 | Jul., 1978 | Schintlmeister | 428/699.
|
| 4226932 | Oct., 1980 | Ferraris | 428/623.
|
| 4720437 | Jan., 1988 | Chudo et al. | 428/699.
|
| 4943486 | Jul., 1990 | Uchiyama | 428/698.
|
| Foreign Patent Documents |
| 2528255 | Feb., 1976 | DE | 428/698.
|
| 70040 | Mar., 1987 | JP | 428/698.
|
| 1601224 | Oct., 1981 | GB | 428/698.
|
Primary Examiner: Andrews; Melvyn J.
Assistant Examiner: Wyszomierski; George
Attorney, Agent or Firm: Kaplan; Blum
Claims
What is claimed is:
1. An ornamental member, comprising:
a substrate;
a first hard film having a hardness of at least about 1000 HV deposited on
said substrate; and
a second hard film having a hardness of at least about 1000 HV selectively
deposited on said first hard film so that portions of the first hard film
are exposed,
said first hard film and said second hard film having different color
tones, at least one of said first hard film and said second hard film is a
Ti containing ceramic and the other of said first hard film and said
second hard film is selected from the group consisting of a Cr containing
ceramic.
2. The ornamental member of claim 1, wherein said Cr containing ceramic
film contains Cr, N and C.
3. The ornamental member of claim 1, wherein said Ti to containing ceramic
are selected from the group consisting of:
a hard film containing Ti and N;
a hard film containing Ti, N and C,
a hard film containing Ti and O,
and a hard film containing Ti, O and C.
4. The ornamental member of claim 1, wherein said first hard film is
between about 0.2 and 1.5 .mu.m thick and said second hard film is between
about 0.2 and 1.5 .mu.m thick.
5. The ornamental member of claim 4, wherein said first hard film is
between about 0.2 and 0.8 .mu.m thick and said second hard film is between
about 0.2 and 0.8 .mu.m thick.
6. The ornamental memeber of claim 1, wherein said ornamental member
presents two color tones and one of said color tones is the color of said
first hard film and the other of said color tones is the color tone of
said second hard film.
7. The ornamental member of claim 1, further including a third hard film
selectively deposited on said second hard film, said third hard film
selected from the group consisting of a Cr containing film and a Ti
containing ceramic film.
8. The ornamental member of claim 7, wherein said first hard film is
between about 0.2 and 1.0 .mu.m thick, said second hard film is between
about 0.2 and 1.0 .mu.m thick and said third hard film is between about
0.2 and 1.0 .mu.m thick.
9. The ornamental member of claim 8, wherein said first hard film is
between about 0.2 and 0.8 .mu.m thick, said second hard film is between
about 0.2 and 0.8 .mu.m thick and said third hard film is between about
0.2 and 0.8 .mu.m thick.
10. The ornamental member of claim 1, further including a third hard film
selectively deposited on said first hard film at a portion at which said
second hard film is not deposited on said first hard film.
11. The ornamental member of claim 10, wherein said first hard film is
between about 0.2 and 1.5 .mu.m thick, said second hard film is between
about 0.2 and 1.5 .mu.m thick, and said third hard film is between about
0.2 and 1.5 .mu.m thick.
12. The ornamental member of claim 11, wherein said first hard film is
between about 0.2 and 0.8 .mu.m thick, said second hard film is between
about 0.2 and 0.8 .mu.m thick and said third hard film is between about
0.2 and 0.8 .mu.m thick.
13. The ornamental member of claim 1, wherein said first hard film is said
Cr containing ceramic film and said second hard film is said Ti containing
ceramic film.
14. The ornamental member of claim 1, wherein said first hard film is a Ti
containing ceramic film and said second hard film is a Cr containing film.
15. The ornamental member of claim 1, wherein said first hard film and said
second hard film are Ti containing ceramic films.
16. The ornamental member of claim 1, further including at least one layer
of undercoat plating deposited on said substrate, said undercoat plating
selected from the group consisting of gold, gold alloy, chromium,
palladium, palladium alloy, rhodium and ruthenium and combinations thereof
with said first hard film deposited on said undercoat plating.
17. The ornamental member of claim 1, further including at least one layer
of a pre-undercoat plating, deposited on the substrate selected from the
group consisting of copper, Ni and Ni alloy, and at least one layer of
undercoat plating deposited on said pre-undercoat plating, said undercoat
plating selected from the group consisting of gold, gold alloy, chromium,
palladium, palladium alloy, rhodium and ruthenium and combinations thereof
with said first hard film deposited on said undercoat plating.
18. The ornamental member of claim 1, wherein the substrate is selected
from the group consisting of stainless steel, a ceramic material, a copper
alloy, a hard Ni-base alloy, a Co-based alloy, zinc, a zinc alloy and a
plastic material.
19. The ornamental member of claim 1, wherein said substrate is SUS 304
stainless steel.
20. The ornamental member of claim 1, wherein said substrate is zinc.
21. The ornamental member of claim 1, wherein said substrate is brass.
Description
BACKGROUND OF THE INVENTION
This invention relates generally to an ornamental member produced by ion
plating and more particularly to a multi-colored ornamental member formed
of a combination of two hard films.
Conventional ornamental members, such as the exterior member of a watch
with a multi-colored surface, include a stainless steel color and at least
gold, dark grey, brown or blue. These generally are prepared by coating
the surface of the ornamental member of a SUS material with a gold film
produced by wet gold plating or ion plating, a dark grey film produced by
wet rhodium or tin-nickel plating, or a brown film or a blue film produced
by ion plating. A conventional exterior ornamental member of a watch with
a two colored surface, including gold and brown or blue is generally
produced by coating the surface of a substrate of the ornamental member
with a gold film by gold or gold alloy wet plating and a brown or blue
hard film produced by ion plating.
These conventional methods, however, suffer from poor scratch resistance,
poor wear resistance and high cost. A partially exposed surface of a SUS
material, which has a hardness of between about 140 and 180 Hv, is
susceptible to scratching. A surface including a partial gold wet plated
surface, which has a hardness of between about 200 and 300 Hv, is also
susceptible to scratching. In order to enhance durability, it is necessary
to increase the thickness of the layer of plating, which disadvantageously
raises the cost of the article. A surface which is also partially wet
plated with rhodium or tin-nickel is also susceptible to scratching. In
addition, a rhodium plated surface is very expensive.
Accordingly, it is desirable to provide an improved ornamental member which
eliminates these problems associated with the prior art and has good
scratch resistance and wear resistance.
SUMMARY OF THE INVENTION
Generally speaking, in accordance with the invention, an improved
ornamental member which has high ornamental value and hard surface has a
substrate coated with a laminate of at least two hard films of Cr or Ti of
different color tones by ion plating to form an ornamental member having a
multi-colored surface. The laminate includes a combination of Cr and Ti
hard films including a stainless steel colored Cr hard film layer
containing Cr, N and C as the main constituents, a gold colored Ti hard
film having Ti and N as the main constituents, a dark grey Ti hard film
having Ti, N and C as the main constituents, a blue Ti hard film having Ti
and 0 as the main constituents and a brown Ti hard film having Ti, 0 and C
as the main constituents. The thickness of a single layer of the hard film
is between about 0.2 and 1.5 .mu.m and the total film thickness at the
laminated portion is less than about 3 .mu.m. Preferably, each hard film
layer is between about 0.2 and 0.8 .mu.m.
An ornamental member including one Cr hard film and one Ti hard film or two
Ti hard film is formed by ion plating a first hard film on a substrate. A
masking material is deposited in a pattern on the first hard film and a
second hard film is ion plated on the first hard film and the masking
material. The masking material is removed, removing the portion of the
second hard film formed over it. Alternately, a first hard film is ion
plated on the substrate and a second hard film is ion plated on the first
hard film and the second hard film is partially removed by etching.
Accordingly, it is an object of this invention to provide an improved
ornamental member having a multi-colored surface.
Another object of the invention is to provide an improved ornamental member
having a high degree of hardness.
A further object of the invention is to provide an improved ornamental
member with excellent scratch resistance, wear resistance and corrosion
resistance.
A still further object of this invention is to provide an improved
ornamental member with excellent adherence.
Yet a further object of this invention is to provide an improved ornamental
member which is low in cost.
Still other objects and advantages of the invention will in part be obvious
and will in part be apparent from the specification.
The invention accordingly comprises the several steps and the relation of
one or more of such steps with respect to each of the others, and the
article possessing the features, properties, and the relation of elements,
which are exemplified in the following detailed disclosure, and the scope
of the invention will be indicated in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
For a fuller understanding of the invention, reference is had to the
following description taken in connection with the accompanying drawing,
in which:
FIGS. 1(a), 1(b), 1(c) and 1(d) are sectional views illustrating the steps
of preparing an ornamental member in accordance with an embodiment of the
invention;
FIGS. 2(a), 2(b), 2(c) and 2(d) are sectional views illustrating the steps
of preparing an ornamental member in accordance with another embodiment of
the invention; and
FIGS. 3-21 are sectional views of an ornamental member in accordance with
further embodiments of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
An ornamental member prepared in accordance with the invention is formed by
a "second-layer ion plating method" or a "second-layer etching method".
The ornamental member prepared by the second-layer ion plating method is
shown in cross section in FIGS. 1(a)-1(d). A first hard film 2 is
laminated on a substrate 1 by ion plating, as shown in FIG. 1(a). The
laminate is baked and hardened. The portion of the surface of first hard
film 2 intended to be visible is coated with an organic coating 3 to mask
first hard film 2 as shown in FIG. 1(b).
A second hard film 4 is disposed across the upper surface by ion plating,
as shown in FIG. 1(c). Substrate 1, including first hard film 2, inorganic
coating 3 and second hard film 4, is immersed in an organic solvent to
dissolve and remove inorganic coating 3 and the portion of second hard
film 4 formed on inorganic coating 3. Thus, a two colored ornamental
member including first hard film 2 and second hard film 4 is obtained as
shown in FIG. 1(d).
Any material that can withstand the high temperature of ion plating may be
used as substrate 1. For example, substrate 1 may be formed from a ceramic
material, a hard Ni-base alloy, a Co-base alloy, stainless steel, a copper
alloy, brass, zinc, a zinc alloy or a plastic material. Preferably,
substrate 1 is SUS 304.
It is necessary for substrate 1 to have sufficient corrosion resistance
prior to coating with the hard film since most of the hard films produced
by ion plating include pinholes. If substrate 1 does not have sufficient
corrosion resistance, it is necessary to form at least one undercoat layer
by plating prior to ion plating first layer hard film 2. If substrate 1 is
formed from a ceramic material, a hard Ni-base alloy, a Co-base alloy,
stainless steel or the like, substrate 1 has good corrosion resistance and
an undercoat plating is not necessary. However, if substrate 1 is a
stainless steel substrate containing a free-cutting ingredient such as
sulfur, substrate 1 is slightly inferior in corrosion resistance. In this
case, it is necessary to laminate a single or several gold-, gold alloy-,
chromium-, palladium-, palladium alloy-, rhodium- or ruthenium-plated
layers as an undercoat to obtain a substrate with sufficient corrosion
resistance.
If substrate 1 is a copper alloy, zinc or a zinc alloy, it is necessary to
deposit a single or several gold-, gold alloy-, chromium-, palladium-,
palladium alloy-, rhodium- or ruthenium-plated layers after laminating a
single or several copper, Ni or Ni alloy layers on substrate 1. If an
undercoat of a copper alloy, zinc or a zinc alloy is formed on substrate 1
prior to ion plating, it is possible to prevent the substrate material
from being exposed directly to high temperature and a high vacuum
atmosphere during ion plating. Thus, a rise in the internal temperature of
the substrate material and the formation of a blister from the
dezincification is prevented.
If substrate 1 is a plastic material, it is generally treated with Ni by
electroless plating prior to undercoat plating in a manner similar to the
undercoat plating of a copper alloy, zinc or a zinc alloy substrate. Since
plastic is an organic material having a low melting point, gas easily
escapes due to a rise in temperature during ion plating, causing frequent
defective adhesion with the ion plated film. Thus, undercoat plating is
essential to prevent defective adhesion.
The undercoat plating is between about 0.2 and 20 .mu.m thick. In terms of
productivity and functional efficiency, the undercoat is preferably
between about 2 and 10 .mu.m thick when the undercoat is formed of a
single layer or is multi-layered. However, there is no difference is
quality when the thickness is between about 0.2 and 20 .mu.m thick.
First hard film 2 and second hard film 4 are formed of compounds including
Cr or Ti. For example, a stainless steel colored hard film may be formed
of a material including Cr, N and C. A gold coated hard film may be formed
of a material including Ti and N. A dark grey hard film may be formed of a
material including Ti, N and C, or Cr, N, C and 0. A blue hard film may be
formed of a material including Ti and 0. A brown colored hard film may be
formed of a compound including Ti, C and 0.
To form a two colored ornamental member in accordance with the invention, a
combination of Cr and Ti hard films is used. For example, first hard film
2 may be a stainless steel colored Cr hard film and second hard film 4 may
be a gold, dark grey, brown or blue colored Ti hard film. Alternatively,
first hard film 2 may be a gold, dark grey, brown or blue colored Ti hard
film and second hard film 4 may be a stainless steel colored Cr hard film.
It is also possible to form a two colored ornamental member from a
combination of Ti hard films. For example, first hard film 2 may be formed
of a gold colored Ti hard film and second hard film 4 may be formed of a
blue or brown colored Ti hard film. Alternatively, first hard film 2 may
be formed of a blue or brown colored Ti hard film and second hard film 4
may be formed of a gold colored Ti hard film.
An ornamental member including three or more colors in accordance with the
invention is formed by combining Cr hard films and Ti hard films having
different color tones.
Although an ion-plated film provides a high degree of hardness, an increase
in the thickness of the hard film results in an increase in internal
stress. Thus, the film becomes unfavorably brittle. To secure the
adherence required for the ornamental member, the thickness of a single
layer of hard film is between about 0.2 and 1.5 .mu.m and the total film
thickness of the laminated portion is less than about 3 .mu.m. Preferably,
a single layer hard film has a thickness between about 0.2 and 0.8 .mu.m.
If a single layer of hard film is less than about 0.2 .mu.m, the scratch
resistance and wear resistance are inferior and predetermined tones cannot
be formed. If the thickness of the laminated portion exceeds about 3
.mu.m, the internal stress lowers the adherence and the film may separate.
The method of forming an ornamental member in accordance with the invention
by the second layer etching method is shown in FIGS. 2(a)-2(d). The second
layer etching method may be used when one film is a Cr hard film and the
other film is a Ti hard film. The second-layer ion plating method may be
used when both films are Ti hard films or when one film is a Ti hard film
and the other film is a Cr hard film.
First hard film 2 is formed on substrate 1 by ion plating, as shown in FIG.
2(a). A second hard film 5 is formed on first hard film 2 by ion plating,
as shown in FIG. 2(b). The laminate is baked and hardened and an organic
coating 6 is deposited on the surface portion of second hard film 5 where
second hard film 5 is intended to be visible on the finished exterior, as
shown in FIG. 2(c).
Substrate 1 including first hard film 2, second hard film 5 and organic
coating 6 is immersed in a remover which dissolves only second hard film
5. Second hard film 5 is dissolved and removed except for the portions
where second hard film 6 is covered with organic coating 6. Substrate 1 is
immersed in an organic solvent to remove organic coating 6. Thus, a two
colored ornamental member in accordance with the invention formed by a
combination of first hard film 2 and second hard film 5 is obtained, as
shown in FIG. 2(d).
As described above, an ornamental member in accordance with the invention
includes at least two hard films of different color tones laminated on a
substrate by ion plating to form an exterior surface including a
multiplicity of colors. The hardness of the substrate of the ornamental
member is not less than 1000 Hv over the entire surface. Thus, the scratch
resistance and wear resistance are superior to those of a conventional
ornamental member.
The following examples are set forth by way of illustration to show
preparation of ornamental members in accordance with the invention. They
are set forth for purposes of illustration only, and not intended in a
limiting sense.
EXAMPLES
One hundred samples, in the shape of an exterior member of a watch, having
two different colored hard films and the structures shown in FIGS. 3
through 14 were prepared. Examples 1 through 60 show coated ornamental
members prepared in accordance with preferred embodiments of the
invention. Comparative Examples 1 through 40 are set forth for purposes of
comparison.
In each example, a first hard film was ion plated on the substrate in the
following manner. A substrate formed of SUS 304, brass or zinc in the
shape of an exterior member of a watch, was inserted into an evacuated ion
plating device. Argon gas was introduced into the device and ion
bombardment was carried out for five minutes with a negative voltage of
0.5 kV applied to the substrate while maintaining the pressure at 0.02
torr. Thus, the surface of substrate 1 was cleaned.
Argon gas was discharged and the pressure of the vacuum chamber was
restored to 1.times.10.sup.-4 torr. Pure Ti or pure Cr was evaporated by
electron beam heating, and a predetermined amount of a reaction gas was
introduced to form a Ti or Cr hard film of an intermetallic compound of
pure Ti or pure Cr and the reaction gas. The reaction gas was N.sub.2 gas,
C.sub.2 H.sub.2 gas and O.sub.2 or gas mixtures including at least one of
these gases. The thickness of the hard film was controlled by the
evaporation time of pure Ti or pure Cr and the tone of the hard film was
controlled by the kind of metal evaporated (Cr or Ti) and the reaction
gas.
In the samples in which the ornamental member was prepared by the second
layer ion plating method, the first hard film formed in the
above-described manner, was coated with an inorganic coating Heat
Resistant Masking Material-D produced by Okuno Seiyaku K.K. at the
portions where the first hard film was intended to be visible as the
exterior coating. The inorganic coating was dried in the manner shown in
Table 13.
A second hard film of Ti or Cr was ion plated over the first hard film and
the inorganic coating material in the same manner as the first hard film
was ion plated over the substrate. The inorganic coating layer was
dissolved by Trichlene ultrasonic cleaning. The portions of the second
hard film covering the inorganic coating were removed upon dissolution of
the inorganic coating material to form the samples of the ornamental
member of Tables 1-12.
In the samples in which the ornamental member was formed by the second
layer etching method, the first hard layer was formed in the
above-described manner by the ion plating method. A second hard film of Ti
or Cr was ion plated over the first hard film in the same manner as the
first hard film was ion plated over the substrate.
SPR-557W, an organic coating material produced by Sanei Kagaku K.K., was
deposited on the second hard film at the portions where the first hard
film was intended to be visible a the exterior coating. The organic
coating was dried in accordance with the procedures specified in Table 13.
The portions of the second hard film not covered by the organic coating
were removed in accordance with the procedure shown in Table 14. The
organic coating was removed by Trichlene ultrasonic cleaning to form the
samples of the ornamental member of Tables 1-12.
When brass and zinc were used as a substrate it was necessary to undercoat
plate the substrate. The structure and the thickness of the undercoat
plating of the Examples of the ornamental member in accordance with the
invention and the Comparative Examples is shown in Table 15.
The conditions used to produce the samples of Examples 1-6 and Comparative
Examples 1-4 having the structures shown in FIG. 3, and the results of
evaluating the samples are shown in Table 1. Each sample included a
stainless steel colored Cr first hard film 7 and a gold colored Ti second
hard film 8 disposed on substrate 1 of SUS 304, brass or zinc.
The conditions used to produce the samples of Examples 7-12 and Comparative
Examples 5-8 having the structure shown in FIG. 4, and the results of
evaluating the samples are shown in Table 2. Each sample included gold
colored Ti first hard film 8 and stainless steel colored Cr second hard
film 7 disposed on substrate 1 of SUS 304, brass or zinc.
The conditions used to produce the samples of Examples 13-18 and
Comparative Examples 9-12 having the structure shown in FIG. 5, and the
results of evaluating the samples are shown in Table 3. Each sample
included stainless steel colored Cr first hard film 7 and a dark grey
colored Ti second hard film 9 disposed on substrate 1 of SUS 304, brass or
zinc.
The conditions used to produce the samples of Examples 19-24 and
Comparative Examples 13-16 having the structure shown in FIG. 6, and the
results of evaluating the samples are shown in Table 4. Each sample
included dark grey colored Ti first hard film 9 and a stainless steel
colored Cr second hard film 7 disposed on substrate 1 of SUS 304, brass or
zinc.
The conditions used to produce the samples of Examples 25-30 and
Comparative Examples 17-20 having the structure shown in FIG. 7, and the
results of evaluating the samples are shown in Table 5. Each sample
included stainless steel colored Cr first hard film 7 and a brown colored
Ti second hard film 10 disposed on substrate 1 of SUS 304, brass or zinc.
The conditions used to produce the samples of Examples 31-36 and
Comparative Examples 21-24 having the structure shown in FIG. 8, and the
results of evaluating the samples are shown in Table 6. Each sample
included brown colored Ti first hard film 10 and stainless steel colored
Cr second hard film 7 disposed on substrate 1 of SUS 304, brass or zinc.
The conditions used to produce the samples of Examples 36-42 and
Comparative Examples 25-28 having the structure shown in FIG. 9, and the
results of evaluating the samples are shown in Table 7. Each sample
included a stainless steel colored Cr first hard film 7 and a blue colored
Ti second hard film 11 disposed on substrate 1 of SUS 304, brass or zinc.
The conditions used to produce the samples of Examples 43-48 and
Comparative Examples 29-32 having the structure shown in FIG. 10, and the
results of evaluating the samples are shown in Table 8. Each sample
included blue colored Ti first hard film 11 and stainless steel colored Cr
second hard film 7 disposed on substrate 1 of SUS 304, brass or zinc.
The conditions used to produce the samples of Examples 49-51 and
Comparative Examples 33-34 having the structure shown in FIG. 11, and the
results of evaluating the samples are shown in Table 9. Each sample
included gold colored Ti first hard film 8 and blue colored Ti second hard
film 11 disposed on substrate 1 of SUS 304, brass or zinc.
The conditions used to produce the samples of Examples 52-54 and
Comparative Examples 35-36 having the structure shown in FIG. 12, and the
results of evaluating the samples are shown in Table 10. Each sample
included blue colored Ti first hard film 11 and a gold colored Ti second
hard film 8 disposed on substrate 1 of SUS 304, brass or zinc.
The conditions used to produce the samples of Examples 55-57 and
Comparative Examples 37-38 having the structure shown in FIG. 13, and the
results of evaluating the samples are shown in Table 11. Each sample
included gold colored Ti first hard film 8 and brown colored Ti second
hard film 10 disposed on substrate 1 of SUS 304, brass or zinc.
The conditions used to produce the samples of Examples 58-60 and
Comparative Examples 58-60 having the structure shown in FIG. 14, and the
results of evaluating the samples are shown in Table 12. Each sample
included brown colored Ti first hard film 10 and gold colored Ti second
hard film 8 disposed on substrate 1 of SUS 304, brass or zinc.
In Tables 1-12, "Processing time (min)" was the time required to deposit
the metal of the evaporation source during ion plating. "Ratio" of gas is
the ratio of the reaction gases used during ion plating. "Gas pressure" is
the pressure in the vacuum tank in a stable state after the introduction
of the reaction gases. Table 16 describes the criteria of properties
evaluated in Tables 1-12.
TABLE 1
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
1 2 3 4 5 6 1 2 3 4
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 2 FIG. 1 FIG. 2
Substrate SUS Brass
Zinc
SUS Brass
Zinc
SUS Brass
SUS Brass
material 304 304 304 304
Undercoat No Yes Yes No Yes Yes No Yes No Yes
plating
Hard film for first
Producing conditions
layer Evaporation Cr Cr Cr Cr Cr Cr Cr Cr Cr Cr
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
N.sub.2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1200
1400
1000
1200
1400
1000
1450
900 1450
900
(HV)
Tone SUS SUS SUS SUS SUS SUS SUS IFC*
SUS IFC*
color
color
color
color
color
color
color color
Hard film for 2nd
Producing conditions
layer Evaporation Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Gas N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
introduced
Gas .multidot. pressure
5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1250
1350
1000
1250
1350
1000
1400
900 1400
900
(HV)
Tone Gold
Deep
Light
Gold
Deep
Light
Gold
IFC*
Gold
IFC*
gold
gold gold
gold
Total film thickness
1.4 3.0 0.4 1.4 3.0 0.4 3.4 0.3 3.4 0.3
Evaluation
Tone .circleincircle.
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.DELTA.
Adherence .circleincircle.
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.circleincircle
.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Generation of an interference color
TABLE 2
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
7 8 9 10 11 12 5 6 7 8
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 2 FIG. 1 FIG. 2
Substrate SUS Brass
Zinc
SUS Brass
Zinc
SUS Brass
SUS Brass
material 304 304 304 304
Undercoat No Yes Yes No Yes Yes No Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Gas N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
introduced
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1250
1350
1000
1250
1350
1000
1400
900 1400
900
(Hv)
Tone Gold
Deep
Light
Gold
Deep
Light
Gold
IFC*
Gold
IFC*
gold
gold gold
gold
Hard film for 2nd
Producing conditions
layer Evaporation Cr Cr Cr Cr Cr Cr Cr Cr Cr Cr
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
N.sub.2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1200
1400
1000
1200
1400
1000
1450
900 1450
900
(HV)
Tone SUS SUS SUS SUS SUS SUS SUS IFC*
SUS IFC*
color
color
color
color
color
color
color color
Total film thickness
1.4 3.0 0.4 1.4 3.0 0.4 3.4 0.3 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
.circleincircle
.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Generation of an interference color
TABLE 3
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
13 14 15 16 17 18 9 10 11 12
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 2 FIG. 1 FIG. 2
Substrate SUS Brass
Zinc
SUS Brass
Zinc
SUS Brass
SUS Brass
material 304 304 304 304
Undercoat No Yes Yes No Yes Yes No Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Cr Cr Cr Cr Cr Cr Cr Cr Cr Cr
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
N.sub. 2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1200
1400
1000
1200
1400
1000
1450
900 1450
900
(HV)
Tone SUS SUS SUS SUS SUS SUS SUS IFC*
SUS IFC*
color
color
color
color
color
color
color color
Hard film for 2nd
Producing conditions
layer Evaporation Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:5 1:5 1:5 1:5 1:5 1:5 1:5 1:5 1:5 1:5
N.sub.2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1200
1300
1000
1200
1300
1000
1350
900 1350
900
(HV)
Tone Dark
Gray
Light
Dark
Gray
Light
Dark
IFC*
Dark
IFC*
gray
black
gray
gray
black
gray
gray gray
Total film thickness
1.4 3.0 0.4 1.4 3.0 0.4 3.4 0.3 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
.circleincircle
.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Generation of an interference color
TABLE 4
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
19 20 21 22 23 24 13 14 15 16
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 2 FIG. 1 FIG. 2
Substrate SUS Brass
Zinc
SUS Brass
Zinc
SUS Brass
SUS Brass
material 304 304 304 304
Undercoat No Yes Yes No Yes Yes No Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:5 1:5 1:5 1:5 1:5 1:5 1:5 1:5 1:5 1:5
N.sub. 2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1200
1300
1000
1200
1300
1000
1350
900 1350
900
(HV)
Tone Dark
Gray
Light
Dark
Gray
Light
Dark
IFC*
Dark
IFC*
gray
black
gray
gray
black
gray
gray gray
Hard film for 2nd
Producing conditions
layer Evaporation Cr Cr Cr Cr Cr Cr Cr Cr Cr Cr
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
N.sub.2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1200
1400
1000
1200
1400
1000
1450
900 1450
900
(HV)
Tone SUS SUS SUS SUS SUS SUS SUS IFC*
SUS IFC*
color
color
color
color
color
color
color color
Total film thickness
1.4 3.0 0.4 1.4 3.0 0.4 3.4 0.3 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
.circleincircle
.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Generation of an interference color
TABLE 5
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
25 26 27 28 29 30 17 18 19 20
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 2 FIG. 1 FIG. 2
Substrate SUS Brass
Zinc
SUS Brass
Zinc
SUS Brass
SUS Brass
material 304 304 304 304
Undercoat No Yes Yes No Yes Yes No Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Cr Cr Cr Cr Cr Cr Cr Cr Cr Cr
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
N.sub. 2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1200
1400
1000
1200
1400
1000
1450
900 1450
900
(HV)
Tone SUS SUS SUS SUS SUS SUS SUS IFC*
SUS IFC*
color
color
color
color
color
color
color color
Hard film for 2nd
Producing conditions
layer Evaporation Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 3:1 3:1 3:1 3:1 3:1 3:1 3:1 3:1 3:1 3:1
N.sub.2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1350
1450
1100
1350
1450
1100
1500
900 1500
900
(HV)
Tone Brown
Dark
Light
Brown
Dark
Light
Brown
IFC*
Brown
IFC*
brown
brown brown
brown
Total film thickness
1.4 3.0 0.4 1.4 3.0 0.4 3.4 0.3 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
.circleincircle
.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Generation of an interference color
TABLE 6
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
31 32 33 34 35 36 21 22 23 24
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 2 FIG. 1 FIG. 2
Substrate SUS Brass
Zinc
SUS Brass
Zinc
SUS Brass
SUS Brass
material 304 304 304 304
Undercoat No Yes Yes No Yes Yes No Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 3:1 3:1 3:1 3:1 3:1 3:1 3:1 3:1 3:1 3:1
N.sub. 2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1350
1450
1100
1350
1450
1100
1500
900 1500
900
(HV)
Tone Brown
Dark
Light
Brown
Dark
Light
Brown
IFC*
Brown
IFC*
brown
brown brown
brown
Hard film for 2nd
Producing conditions
layer Evaporation Cr Cr Cr Cr Cr Cr Cr Cr Cr Cr
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
N.sub.2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1200
1400
1000
1200
1400
1000
1450
900 1450
900
(HV)
Tone SUS SUS SUS SUS SUS SUS SUS IFC*
SUS IFC*
color
color
color
color
color
color
color color
Total film thickness
1.4 3.0 0.4 1.4 3.0 0.4 3.4 0.3 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
.circleincircle
.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Generation of an interference color
TABLE 7
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
37 38 39 40 41 42 25 26 27 28
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 2 FIG. 1 FIG. 2
Substrate SUS Brass
Zinc
SUS Brass
Zinc
SUS Brass
SUS Brass
material 304 304 304 304
Undercoat No Yes Yes No Yes Yes No Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Cr Cr Cr Cr Cr Cr Cr Cr Cr Cr
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
N.sub. 2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu. m)
Hardness 1200
1400
1000
1200
1400
1000
1450
900 1450
900
(HV)
Tone SUS SUS SUS SUS SUS SUS SUS IFC*
SUS IFC*
color
color
color
color
color
color
color color
Hard film for 2nd
Producing conditions
layer Evaporation Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Gas O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
introduced
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1350
1450
1100
1350
1450
1100
1500
900 1500
900
(HV)
Tone Blue
Dark
Light
Blue
Dark
Light
Blue
IFC*
Blue
IFC*
blue
blue blue
blue
Total film thickness
1.4 3.0 0.4 1.4 3.0 0.4 3.4 0.3 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
.circleincircle
.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Generation of an interference color
TABLE 8
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
43 44 45 46 47 48 29 30 31 32
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 2 FIG. 1 FIG. 2
Substrate SUS Brass
Zinc
SUS Brass
Zinc
SUS Brass
SUS Brass
material 304 304 304 304
Undercoat No Yes Yes No Yes Yes No Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Gas O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
introduced
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1350
1450
1100
1350
1450
1100
1500
900 1500
900
(HV)
Tone Blue
Dark
Light
Blue
Dark
Light
Blue
IFC*
Blue
IFC*
blue
blue blue
blue
Hard film for 2nd
Producing conditions
layer Evaporation Cr Cr Cr Cr Cr Cr Cr Cr Cr Cr
source
Processing 7 15 2 7 15 2 17 1.5 17 1.5
time (min)
Ratio of 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
N.sub.2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9 2 5 9 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 0.7 1.5 0.2 1.7 0.15
1.7 0.15
(.mu.m)
Hardness 1200
1400
1000
1200
1400
1000
1450
900 1450
900
(HV)
Tone SUS SUS SUS SUS SUS SUS SUS IFC*
SUS IFC*
color
color
color
color
color
color
color color
Total film thickness
1.4 3.0 0.4 1.4 3.0 0.4 3.4 0.3 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
.circleincircle
.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle
.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Generation of an interference color
TABLE 9
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
49 50 51 33 34
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 1
Substrate SUS Brass
Zinc
SUS Brass
material 304 304
Undercoat No Yes Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Pure
Pure
Pure
Pure
Pure
source Ti Ti Ti Ti Ti
Processing 7 15 2 17 1.5
time (min)
Gas N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
introduced
Gas pressure 5 9 2 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 1.7 0.15
(.mu.m)
Hardness 1250
1350
1000
1400
900
(HV)
Tone Gold
Deep
Light
Gold
IFC*
gold
gold
Hard film for 2nd
Producing conditions
layer Evaporation Pure
Pure
Pure
Pure
Pure
source Ti Ti Ti Ti Ti
Processing 7 15 2 17 1.5
time (min)
Gas O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
introduced
Gas pressure 5 9 2 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 1.7 0.15
(.mu.m)
Hardness 1350
1450
1100
1500
900
(HV)
Tone Blue
Dark
Light
Blue
IFC*
blue
blue
Total film thickness
1.4 3.0 0.4 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Interference color
TABLE 10
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
52 53 54 35 36
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 1
Substrate SUS Brass
Zinc
SUS Brass
material 304 304
Undercoat No Yes Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Pure
Pure
Pure
Pure
Pure
source Ti Ti Ti Ti Ti
Processing 7 15 2 17 1.5
time (min)
Gas O.sub.2
O.sub.2
O.sub.2
O.sub.2
O.sub.2
introduced
Gas pressure 5 9 2 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 1.7 0.1
(.mu.m)
Hardness 1350
1450
1100
1500
900
(HV)
Tone Blue
Dark
Light
Blue
IFC*
blue
blue
Hard film for 2nd
Producing conditions
layer Evaporation Pure
Pure
Pure
Pure
Pure
source Ti Ti Ti Ti Ti
Processing 7 15 2 17 1.5
time (min)
Gas N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
introduced
Gas pressure 5 9 2 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 1.7 0.1
(.mu.m)
Hardness 1250
1350
1000
1400
900
(HV)
Tone Gold
Deep
Light
Gold
IFC*
gold
gold
Total film thickness
1.4 3.0 0.4 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Interference color
TABLE 11
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
55 56 57 37 38
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 1
Substrate SUS Brass
Zinc
SUS Brass
material 304 304
Undercoat No Yes Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Pure
Pure
Pure
Pure
Pure
source Ti Ti Ti Ti Ti
Processing 7 15 2 17 1.5
time (min)
Gas N.sub.2
N.sub.2
N.sub.2
N.sub.2
N.sub.2
introduced
Gas pressure 5 9 2 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 1.7 0.15
(.mu.m)
Hardness 1250
1350
1000
1400
900
(HV)
Tone Gold
Deep
Light
Gold
IFC*
gold
gold
Hard film for 2nd
Producing conditions
layer Evaporation Pure
Pure
Pure
Pure
Pure
source Ti Ti Ti Ti Ti
Processing 7 15 2 17 1.5
time (min)
Ratio of 3:1 3:1 3:1 3:1 3:1
O.sub.2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 1.7 0.15
(.mu.m)
Hardness 1350
1450
1100
1500
900
(HV)
Tone Brown
Dark
Light
Brown
IFC*
brown
brown
Total film thickness
1.4 3.0 0.4 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Interference color
TABLE 12
__________________________________________________________________________
Example and Invention Comparison
Comparative Example No.
58 59 60 39 40
__________________________________________________________________________
Method shown in
FIG. 1 FIG. 1
Substrate SUS Brass
Zinc
SUS Brass
material 304 304
Undercoat No Yes Yes No Yes
plating
Hard film for 1st
Producing conditions
layer Evaporation Pure
Pure
Pure
Pure
Pure
source Ti Ti Ti Ti Ti
Processing 7 15 2 17 1.5
time (min)
Ratio of 3:1 3:1 3:1 3:1 3:1
O.sub.2 :C.sub.2 H.sub.2
Gas pressure 5 9 2 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 1.7 0.15
(.mu.m)
Hardness 1350
1450
1100
1500
900
(HV)
Tone Brown
Dark
Light
Brown
IFC*
brown
brown
Hard film for 2nd
Producing conditions
layer Evaporation Pure
Pure
Pure
Pure
Pure
source Ti Ti Ti Ti Ti
Processing 7 15 2 17 1.5
time (min)
Gas N.sub.2
N.sub. 2
N.sub.2
N.sub.2
N.sub.2
introduced
Gas pressure 5 9 2 5 9
(.times. 10.sup.-4 Torr)
Film
characteristics
Thickness 0.7 1.5 0.2 1.7 0.15
(.mu.m)
Hardness 1250
1350
1000
1400
900
(HV)
Tone Gold
Deep
Light
Gold
IFC*
gold
gold
Total film thickness
1.4 3.0 0.4 3.4 0.3
Evaluation
Tone .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
Adherence .circleincircle.
.circle.
.circleincircle.
.DELTA.
.circleincircle.
Wear resistance
.circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
Corrosion resistance
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
sweat
Artificial .circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
.circleincircle.
Sea water
Hardness .circleincircle.
.circleincircle.
.circle.
.circleincircle.
.DELTA.
__________________________________________________________________________
*IFC: Interference color
TABLE 13
______________________________________
Condition
Trade name Drying Removing
______________________________________
Organic SPR-557W Natural Trichlene
coating (Sanei Kagaku
drying ultrasonic
K.K.) 30 to 60 min
cleaning
Hot-air
drying 150.degree. C.
30 min
Inorganic Heat-resistant
Natural Trichlene
coating masking drying ultrasonic
material-D 30 to 60 min
cleaning
(Okuno Seiyaku
Hot-air
K.K.) drying 200.degree. C.
60 min
______________________________________
TABLE 14
______________________________________
Condition
Composition of
Hard film remover Method
______________________________________
Ti hard film 47% HF 1 vol Temp.: normal
61% HNO.sub.3
1 vol temperature
Immersing time:
10 min.
Cr hard film not less than Temp.: normal
90% H.sub.3 PO.sub.4
temperature
Anodic
electrolysis:
5V .times. 5 min
______________________________________
TABLE 15
__________________________________________________________________________
FIG. No. Structure and thickness
Sample 3 4 5 6 7 8 9 10
11
12
13
14
of undercoat plating
__________________________________________________________________________
Example No.
2 8
14
20
26
32
38
44
50
53
56
59
Cu(4 .mu.m) + Ni(4 .mu.m) + 80 wt %
Pd--Ni (3 .mu.m)
5 11
17
23
29
35
41
47 Cu(4 .mu.m) + Ni(4 .mu.m) + 80 wt %
Pd--Ni (3 .mu.m)
3 9
15
21
27
33
39
45
51
54
57
60
Cu(15 .mu.m) + Ni(10 .mu.m) + 80 wt %
Pd--Ni (3 .mu.m)
6 12
18
24
30
36
42
48 Cu(15 .mu.m) + Ni(10 .mu.m) + 80 wt %
Pd--Ni (3 .mu.m)
Comparative
2 6
10
14
18
22
26
30
34
36
38
40
Cu(4 .mu.m) + Ni(4 .mu.m) + 80 wt %
Pd--Ni (3 .mu.m)
Example No.
4 8
12
16
20
24
28
32 Cu(15 .mu.m) + Ni(10 .mu.m) + 80 wt %
Pd--Ni (3 .mu.m)
__________________________________________________________________________
Criteria of properties evaluated in Tables 1 to 12 are shown in Table 16.
TABLE 16
__________________________________________________________________________
Properties Wear Corrosion
Hardness
Mark Tone resistance
Adherence
resistance
(HV)
__________________________________________________________________________
.circleincircle.
Intended
Not worn
No separation
No corrosion
Not less than 1200
tone
.circle.
Substantially
Little worn
Almost no
Almost no
Less than 1200 to
intended tone
No exposure
separation
corrosion
not less than 1000
.DELTA.
Slight devia-
Partial
Slight or
Slight or
Less than 1000 to
tion from
exposure of
partial
partial
not less than 900
intended tone
material
separation
corrosion
.times.
Considerable
Exposure of
Separation
Corrosion
Less than 900
deviation from
material
over the
over the
intended tone
over the
entire or
entire or
entire considerable
considerable
surface
portion
portion
__________________________________________________________________________
The thicknesses of the ion-plated films were determined using x-ray
analysis. The tone visibly was judged and hardness was measured by a micro
Vickers hardness testing machine with a load of 10 g. In order to examine
wear resistance, the side surface of a watch case was reciprocated 30,000
times, at a stroke of 10 cm, while applying a load of 500 g to the watch
case in close contact with cow leather. The degree of wear of the side
surface of watch case was observed and recorded.
A compression load was applied to the watch case from both ends by a vice
to bend an ornamental member in the shape of a watch exterior member. The
bent portion had an angle of not less than 90.degree., and the degree of
separation of the hard film at the bent portion was examined to determine
adherence. To measure resistance to corrosion the ornamental member was
immersed in artificial sweat and artificial sea water (3% NaCl) for twenty
hours at a temperature of 40.degree. C. and a humidity of 90%. Corrosion
and color change were examined.
In Examples 1-60 showing ornamental members prepared in accordance with the
invention, each ornamental member including a Cr hard film and a Ti hard
film included two color tones having high ornamental value. No corrosion
was observed in the corrosion resistance tests using artificial sweat and
artificial sea water.
In the adherence test, the adherence was sufficient for an exterior member
of a watch in each of Examples 1-60. When the thickness of a single layer
of a hard film exceeded 1.5 .mu.m and the total film thickness exceeded
3.0 .mu.m, as in Comparative Examples 1, 3, 5, 7, 9, 11, 13, 15, 17, 19,
21, 23, 25, 27, 29, 31, 33, 35, 37 and 39, the adherence was reduced and
partial separation between the hard films was observed. Thus, a single
layer of hard film is preferably not more than about 1.5 .mu.m to obtain
sufficient adherence.
On the other hand, when the thickness of single layer or a hard film was
less than 0.2 .mu.m, as in Comparative Examples 2, 4, 6, 8, 10, 12, 14,
16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38 and 40, an interference
color, color shading or partial color change occurred, and it was
impossible to achieve external tone stability. In addition, it was not
possible to obtain the necessary wear resistance from a hard film less
than about 0.2 .mu.m since such a thin film does not have a hardness of
1000 Hv. Thus, the thickness of a single layer of hard film is between
about 0.2 and 1.5 .mu.m and preferably between about 0.2 and 0.8 .mu.m to
obtain sufficient adherence, tone stability and wear resistance.
When the surface of an ornamental member prepared in accordance with the
invention is subject to various treatments, such as stripe patterning,
check patterning, pear-skin patterning and mirror polishing, and hard
films are formed thereon in accordance with the invention, the exterior
can also present the same ornamentality of the surface treatment as the
surface with no hard films formed thereon. If a hard film is further
subjected to polishing by a polishing disk or the like, it is possible to
produce lustrous exterior with high ornamentality. The surface of the
polished hard film has a hardness of not less than 1000 Hv, and no
exposure of the material was observed in wear resistance test.
In Examples 1-60, the general tendency was that the tone became darker with
an increase in gas pressure, while the tone became lighter with a drop in
gas pressure. However, the variation was small enough to judge the tones
as identical in external appearance. Thus, the ornamental members prepared
in accordance with the invention can be used as an exterior member for all
parts or specifics parts of a watch.
Ion plating was carried out under constant conditions to control and
maintain a constant tone of the hard film in Examples 1-60 set forth in
Tables 1-12. Thus, the type of reaction gas, gas flow ratio, the gas
pressure, the amount of evaporation of Ti or Cr and the processing time
were kept constant. When ten samples formed separately from each other
under the same conditions were compared visually and by color-difference
meter, no difference was observed. Thus, the method of forming an
ornamental member in accordance with the invention has high repetitional
precision.
In another embodiment of the invention, a multi-colored ornamental member
includes three or more color tones on a substrate as illustrated in FIGS.
15-21. A Cr or Ti hard film 12 of a color A, a Cr or Ti hard film 13 of a
color B, a Cr or Ti hard film 14 of a color C and a Cr or Ti hard film 15
of a color D are laminated on substrate 1.
In particular, hard film 12 may be a Ti hard film, hard film 13 may be a Ti
hard film of a different color than that of hard film 12, hard film 14 may
be a Cr hard film and hard film 15 may be a Ti hard film of a different
color than that of hard films 12 and 13.
A gold colored hard film may be formed of a material including Ti and N, a
dark grey hard film may be formed of a material including Ti, N and C, a
blue hard film may be formed of a material including Ti and O and a brown
colored hard film may be formed of a compound including Ti, C and O. A
stainless steel colored hard film may be formed of a material including
Cr, N and C. Each of the hard films described above may be used to form
the multi-colored ornamental member in accordance with the invention.
Appropriate combinations of the second-layer ion plating method shown in
FIG. 1 and the second-layer etching method shown in FIG. 2 easily produce
ornamental members including three visible color tones under the same
conditions as those described in Tables 1-12. Corrosion resistance, wear
resistance, color tone and adherence are all satisfactory.
In the embodiments depicted in FIGS. 18, 19 and 21, when the total
thickness of the three hard films exceeded about 3.0 .mu.m, the adherence
of the three layered portion was lowered in the same manner as in
Comparative Examples 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27,
29, 31, 33, 35, 37, and 39. Thus, the thickness of each hard film is
between about 0.2 and 1.5 .mu.m. Preferably, the thickness of each hard
layer is between about 0.2 and 0.8 .mu.m.
The method for forming an ornamental member in accordance with the
invention is not limited to exterior members of watches. Ornaments and
accessories, including frames for glasses, lighter cases, ornamental
bands, buckles, tiepins, rings and utensils, may be formed by the
above-described method. In sum, an ornamental member in accordance with
the invention includes at least two hard films of different colors to
create a multi-colored exterior surface. The hard films have a hardness of
not less than about 1000 Hv and include a stainless steel colored film, a
gold colored film, a dark grey film, a blue film and a brown film.
High ornamental and functional value is obtained by a combination of hard
films of at least two colors, including gold and brown, gold and blue,
stainless steel and gold, stainless steel and dark grey, and stainless
steel and brown. The adherence of the hard layers to the substrate and to
each other, and the scratch resistance, the wear resistance and the
corrosion resistance are superior to those of a conventional ornamental
member.
In a first method of forming an ornamental member in accordance with the
invention, including one Cr hard film and one Ti hard film or two Ti hard
film, a first hard film is ion plated on a substrate. A heat resistant
masking material is deposited in a pattern on the first hard film and
baked and a second hard film is ion plated on the first hard film and the
masking material. The masking material is removed, removing the portion of
the second hard film formed over it. It is possible to choose the
structures of the hard films to reduce the masking area and the masking
time, thus, reducing the cost.
In a second method for forming an ornamental member in accordance with the
invention, including one Cr hard film and one Ti hard film, a first hard
film is ion plated on a substrate. A second hard film is ion plated on the
first hard film and the second hard film is partially removed by etching.
However, when two Ti hard films of different colors are used as the first
hard film and the second hard film, it is difficult to form an ornamental
member in accordance with the invention using the second-layer etching
method.
It will thus be seen that the objects set forth above, among those made
apparent from the preceding description, are efficiently attained and,
since certain changes may be made in carrying out the above method and in
the article set forth without departing from the spirit and scope of the
invention, it is intended that all matter contained in the above
description and shown in the accompanying drawings shall be interpreted as
illustrative and not in a limiting sense.
It is also to be understood that the following claims are intended to cover
all of the generic and specific features of the invention herein described
and all statements of the scope of the invention which, as a matter of
language, might be said to fall therebetween.
Particularly it is to be understood that in said claims, ingredients or
compounds recited in the singular are intended to include compatible
mixtures of such ingredients wherever the sense permits.
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